Composition for semiconductor device processing, method for manufacturing modified substrate, method for manufacturing laminate, and method for manufacturing electronic device

Abstract

The present invention provides a composition for semiconductor device processing, which is capable of forming a film that has excellent ALD inhibition properties and is easily removed by removal processing after ALD processing. The present invention also provides: a method for manufacturing a modified substrate; a method for manufacturing a laminate; and a method for manufacturing an electronic device. A composition for semiconductor device processing according to the present invention contains a compound which has at least one specific functional group that interacts with a substrate. The molecular weight of the compound is 2,000 or less. ClogP of the molecular structure of the compound excluding the specific functional group is 10.3 or more. The specific functional group is a basic functional group or an acidic functional group. In cases where the specific functional group is the basic functional group, the acid dissociation constant of a conjugate acid of the compound, which is obtained by adding protons to the basic functional group, is 7.0 or more. In cases where the specific functional group is the acidic functional group, the acid dissociation constant of the compound is 5.0 or less when protons are dissociated from the acidic functional group.

Description

Composition for treating semiconductor devices, method for manufacturing modified substrates, method for manufacturing laminates, and method for manufacturing electronic devices

[0001] The present invention relates to a composition for treating semiconductor devices, a method for producing a modified substrate, a method for producing a laminate, and a method for producing an electronic device.

[0002] As semiconductor devices become more powerful, smaller and more precise semiconductor elements are required. Traditionally, top-down photolithography has been used to form semiconductor elements, but achieving the required precision is becoming increasingly difficult due to mechanical and optical factors, etc. Therefore, as a bottom-up method for forming semiconductor elements, a method for selectively modifying a substrate has been considered, in which a film of a compound is formed on a region of a substrate made of a specific material by selectively adsorbing the compound to the specific material, and the film is then used to modify regions of the substrate other than the region made of the specific material. Specifically, for example, a method has been devised in which a material that selectively adsorbs to a specific component is used to selectively form a coating that inhibits material deposition on a specific region of the substrate surface, followed by atomic layer deposition (ALD) processing to selectively deposit material in regions where the coating is not present, thereby modifying the substrate.

[0003] As a method for selectively modifying a substrate as described above, Patent Document 1 describes a chemical solution containing a compound A having a specific functional group, an organic solvent, and a specific metal atom, wherein the content of the compound A is more than 10 ppm by mass with respect to the total mass of the chemical solution, the total content of the specific metal atoms is 1000 ppt by mass or less with respect to the total mass of the chemical solution, and the mass ratio of the content of the compound A to the content of the specific metal atoms is 10 ４ ~10 ９ "A method for producing a modified substrate using a chemical solution in which the water content in the chemical solution is 1 mass % or less."

[0004] International Publication No. 2023 / 136042

[0005] The coating used for selectively modifying a substrate as described above is required to suppress the amount of material deposited on the coating when subjected to atomic layer deposition (ALD) processing, i.e., to have excellent ALD inhibition properties. The present inventors formed a coating using the composition disclosed in Patent Document 1 and subjected the coating to ALD processing, and found that there is room for further improvement in ALD inhibition properties. Furthermore, it is also desired that the coating be easily removed by a removal process (particularly a plasma removal process) after the ALD processing.

[0006] Therefore, an object of the present invention is to provide a composition for semiconductor device treatment that has excellent ALD inhibitory properties and can form a coating that is easily removed in a removal treatment after the ALD treatment. Another object of the present invention is to provide a method for producing a modified substrate, a method for producing a laminate, and a method for producing an electronic device.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the problems can be solved by the following configuration.

[0008] [1] A composition for treating semiconductor devices, comprising a compound having at least one specific functional group that interacts with a substrate, wherein the molecular weight of the compound is 2000 or less, the molecular structure of the compound excluding the specific functional group has a ClogP of 10.3 or more, the specific functional group is a basic functional group or an acidic functional group, and when the specific functional group is a basic functional group, the acid dissociation constant of a conjugate acid of the compound obtained by adding a proton to the basic functional group is 7.0 or more, and when the specific functional group is an acidic functional group, the acid dissociation constant of the compound upon dissociation of a proton from the acidic functional group is 5.0 or less. [2] The composition for treating semiconductor devices according to [1], further comprising a solvent. [3] The composition for treating semiconductor devices according to [1] or [2], wherein the specific functional group is the basic functional group, and the basic functional group is an amino group, a hydrazine group, or a guanidine group. [4] The composition for treating a semiconductor device according to any one of [1] to [3], wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group. [5] The composition for treating a semiconductor device according to any one of [1] to [4], wherein the basic functional group is a primary amino group. [6] The composition for treating a semiconductor device according to [1] or [2], wherein the specific functional group is the acidic functional group, and the acidic functional group is a phosphonic acid group, a phosphate group, a phosphinic acid group, a sulfo group, or a carboxy group. [7] The composition for treating a semiconductor device according to [6], wherein the acidic functional group is a phosphonic acid group, a phosphate group, or a sulfo group. [8] The composition for treating a semiconductor device according to any one of [1] to [7], wherein the molecular weight of the compound is 500 or more. [9] The composition for treating a semiconductor device according to any one of [1] to [8], wherein the compound has at least one of an aliphatic hydrocarbon structure and an aromatic ring structure.

[10] The composition for treating a semiconductor device according to any one of [1] to [9], wherein the compound has both an aliphatic hydrocarbon structure and an aromatic ring structure.

[11] The compound is a compound represented by general formula (1), and X in the compound represented by general formula (1) １The composition for treating a semiconductor device according to any one of [1] to

[10] , wherein the ClogP of the molecular structure excluding X is 10.3 or more, and the molecular weight of the compound represented by general formula (1) is 500 to 2000.

[12] The compound is a compound represented by general formula (2), and X in the compound represented by general formula (2) １ The composition for treating a semiconductor device according to any one of [1] to

[10] , wherein the ClogP of the molecular structure excluding (a) is 10.3 or more, and the molecular weight of the compound represented by general formula (2) is 500 to 2000.

[13] The composition for treating a semiconductor device according to any one of [1] to

[12] , wherein the total amount of the compound and the solvent is 99.90 mass % or more based on the total mass of the composition for treating a semiconductor device.

[14] The composition for treating a semiconductor device according to any one of [1] to

[13] , wherein a film obtained by applying the composition for treating a semiconductor device has a water contact angle of 60 degrees or more.

[15] A method for producing a modified substrate, comprising the step of contacting a substrate with the composition for treating a semiconductor device according to any one of [1] to

[14] to form a coating on the substrate.

[16] A method for producing a laminate, comprising: Step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, made of different materials, with the composition for treating semiconductor devices according to any one of [1] to

[14] to form a first coating on the first surface; and Step 2 of subjecting the substrate obtained in Step 1 to atomic layer deposition to form a second coating on the second surface.

[17] A method for producing a laminate according to

[16] , wherein the first surface is a metal surface made of at least one metal selected from copper, cobalt, tungsten, molybdenum, and ruthenium.

[18] A method for producing an electronic device, comprising the method for producing a modified substrate according to

[15] .

[0009] According to the present invention, there is provided a composition for semiconductor device treatment that has excellent ALD inhibitory properties and can form a coating that is easily removed in a removal treatment after the ALD treatment. The present invention also provides a method for producing a modified substrate, a method for producing a laminate, and a method for producing an electronic device.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. In this specification, "ppm" means "parts-per-million (10 －６ ) and "ppb" stands for "parts-per-billion (10 －９ ) and "ppt" stands for "parts-per-trillion (10 －１２ In this specification, when two or more types of a component are present, the "content" of the component means the total content of those two or more components.

[0012] In the present specification, when there are multiple substituents, linking groups, etc. (hereinafter referred to as "substituents, etc.") represented by a specific symbol, or when multiple substituents, etc. are simultaneously specified, this means that the respective substituents, etc. may be the same or different from each other. The same applies to the specification of the number of substituents, etc. The compounds described in the present specification may contain structural isomers, optical isomers, and isotopes, unless otherwise specified. Furthermore, one type of structural isomer, optical isomer, and isotope may be contained alone, or two or more types may be contained. In the present specification, unless otherwise specified, the bonding direction of a divalent group (e.g., -CO-O-) is such that when Y in a compound represented by "X-Y-Z" is -CO-O-, the compound may be either "X-O-CO-Z" or "X-CO-O-Z."

[0013] In this specification, unless otherwise specified, the molecular weight of a compound having a molecular weight distribution is a weight average molecular weight. Furthermore, in this specification, unless otherwise specified, the weight average molecular weight (Mw), number average molecular weight (Mn), and polydispersity index (PDI; Poly Dispersity Index) (Mw / Mn) of a polymer are defined as polystyrene equivalent values ​​measured by GPC (Gel Permeation Chromatography) using a GPC (HLC-8120GPC, manufactured by Tosoh Corporation) apparatus (solvent: tetrahydrofuran, flow rate (sample injection amount): 10 μL, column: TSK gel Multipore HXL-M (manufactured by Tosoh Corporation), column temperature: 40 ° C., flow rate: 1.0 mL / min, detector: differential refractive index detector (Refractive Index Detector)).

[0014] In this specification, ClogP refers to the calculated value of the common logarithm logP of the partition coefficient P between 1-octanol and water. Known methods and software can be used to calculate ClogP, but unless otherwise specified, in the present invention, structures are drawn using ChemDraw Professional (version 20.1.1.1) manufactured by PerkinElmer, and values ​​calculated using the above software package 1 are used. Software package 1: Advanced Chemistry Development (ACD / Labs) Software V20.1.1 for Solaris (1994-2007 ACD / Labs)

[0015] In this specification, pKa is a value calculated using the above software package 1 based on a database of Hammett's substituent constants and known literature values. If pKa cannot be calculated by the above method, a value calculated by a molecular orbital calculation method is used. As a specific method using a molecular orbital calculation method, a value obtained using Gaussian 16 based on DFT (density functional theory) is used.

[0016] [Composition for Treating Semiconductor Devices] The composition of the present invention (hereinafter also referred to as "the composition") is described in detail below. The composition is a composition for treating semiconductor devices, containing a compound having at least one specific functional group that interacts with a substrate (hereinafter also referred to as "the specific compound"), wherein the molecular weight of the specific compound is 2000 or less, the ClogP of the molecular structure of the specific compound excluding the specific functional group is 10.3 or more, the specific functional group is a basic functional group or an acidic functional group, and when the specific functional group is a basic functional group, the acid dissociation constant of the conjugate acid of the compound obtained by adding a proton to the basic functional group is 7.0 or more, and when the specific functional group is an acidic functional group, the acid dissociation constant of the compound when a proton dissociates from the acidic functional group is 5.0 or less.

[0017] Although the reason why the composition having the above-described structure can solve the problem of the present invention is not entirely clear, the inventors speculate as follows. Note that the following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. The specific functional group possessed by the specific compound can bind to or adsorb to the surface of a substrate, such as a metal surface, and therefore a coating can be formed using the composition of the present invention. Furthermore, the molecular structure of the specific compound excluding the specific functional group has a ClogP of 10.3 or more, which is relatively highly hydrophobic, and therefore the formed coating has a high effect of inhibiting film formation by ALD processing. Furthermore, since the molecular weight of the specific compound is within a predetermined range, the formed coating exhibits the effect of inhibiting film formation by ALD processing while being easily removed in a removal process after ALD processing. As described above, it is speculated that the problem of the present invention can be solved by the specific compound having the above-described structure. Hereinafter, obtaining at least one of the effects of superior ALD inhibition and greater ease of removal of the coating (composition) in a removal process after ALD processing is also referred to as "excellent effect of the present invention."

[0018] [Specific Compound] The composition contains a specific compound. The molecular weight of the specific compound is 2000 or less. The molecular weight of the specific compound is not particularly limited as long as it is within the above range, but the upper limit is preferably 1500 or less, more preferably less than 1500, and even more preferably 1000 or less. The lower limit is preferably 300 or more, more preferably 500 or more.

[0019] As described above, the ClogP of the molecular structure excluding the specific functional group in the specific compound is 10.3 or more. The ClogP of the molecular structure is not particularly limited as long as it is within the above range, but is preferably 13.0 or more, more preferably 14.0 or more, and even more preferably 15.0 or more. The upper limit is not particularly limited, and examples include 65.0 or less. Note that the molecular structure excluding the specific functional group in the specific compound means, for example, when the specific compound is E-1 below, the specific functional group in E-1 is -NH ２ Therefore, this -NH ２ The molecular structure excluding the specific functional group in the specific compound corresponds to the "molecular structure excluding the specific functional group in the specific compound."

[0020]

[0021] In order for the molecular structure to fall within a predetermined ClogP range, it is preferable that the specific compound further has a hydrophobic structure. That is, it is preferable that the specific compound has a hydrophobic structure (for example, an aliphatic hydrocarbon structure and an aromatic ring structure, which will be described later) as a partial structure. Examples of hydrophobic structures include an aliphatic hydrocarbon structure and an aromatic ring structure. In other words, it is preferable that the specific compound has at least one of an aliphatic hydrocarbon structure and an aromatic ring structure, and it is more preferable that the specific compound has both an aliphatic hydrocarbon structure and an aromatic ring structure.

[0022] The aliphatic hydrocarbon structure may be linear, branched, or cyclic. The aliphatic hydrocarbon structure may be a monovalent group or a divalent or higher group. Examples of the aliphatic hydrocarbon structure include an alkyl group, an alkenyl group, and an alkynyl group. The number of carbon atoms in the linear or branched aliphatic hydrocarbon structure is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 18. The cyclic aliphatic hydrocarbon structure may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The number of carbon atoms in the cyclic aliphatic hydrocarbon structure is preferably 6 to 30, more preferably 7 to 30, and even more preferably 8 to 20.

[0023] The aromatic ring constituting the aromatic ring structure may be either a monocycle or a polycycle. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, but is preferably an aromatic hydrocarbon ring. The number of carbon atoms in the aromatic ring is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 15. Specific examples of the aromatic ring include a benzene ring, a naphthalene ring, a pyrene ring, a thiophene ring, an indole ring, a carbazole ring, a benzothiophene ring, a dibenzothiophene ring, a porphyrin ring, a 9,9-bisphenylfluorene ring, and an aromatic ring formed by connecting two or more of these rings with a single bond.

[0024] <Specific Functional Group> As described above, the specific compound has at least one specific functional group that interacts with the substrate. The number of specific functional groups possessed by the specific compound is preferably 1 to 3, and more preferably 1 or 2. Specific examples of the interaction between the specific functional group and the substrate include, for example, a covalent bond, a coordinate bond, an ionic bond, a hydrogen bond, an acid-base interaction, a van der Waals bond, and a metallic bond. When the composition is used to form a coating on a metal surface A of a substrate composed of a material containing metal atoms, a coordinate bond or an ionic bond is preferred, and a coordinate bond is more preferred. When the composition is used to form a coating on a non-metal surface B of a substrate composed of a non-metal material, a hydrogen bond, an acid-base interaction, or a covalent bond is preferred. Details of the substrate and the surface of the substrate will be described later.

[0025] The specific functional group is preferably either a group that bonds to or adsorbs onto a metal surface A of the substrate (also referred to as "specific functional group A") or a group that bonds to or adsorbs onto a non-metal surface B of the substrate (also referred to as "specific functional group B"), and is more preferably the specific functional group A. The specific functional group A is preferably a functional group that can form a coordinate bond with a metal.

[0026] As described above, the specific functional group is a basic functional group or an acidic functional group. When the specific functional group is a basic functional group, the acid dissociation constant of the conjugate acid of the compound obtained by adding a proton to the basic functional group is 7.0 or more. When the specific functional group is an acidic functional group, the acid dissociation constant of the compound when a proton dissociates from the acidic functional group is 5.0 or less. When the specific functional group is a basic functional group, the acid dissociation constant of the conjugate acid of the specific compound obtained by adding a proton to the basic functional group is preferably 7.5 or more, more preferably 8.0 or more, and even more preferably 9.0 or more. An upper limit of the acid dissociation constant is, for example, 30.0 or less. When the specific functional group is an acidic functional group, the acid dissociation constant of the specific compound when a proton dissociates from the acidic functional group is preferably 4.5 or less, more preferably 4.0 or less, and even more preferably 3.0 or less. An example of a lower limit is -5.0 or more.

[0027] Examples of the basic functional group include a nitrogen-containing group. Examples of the nitrogen-containing group include an amino group (—NR Ｎ ２ ), quaternary ammonium group (-N ＋ R Ｎ ３ ), a hydrazine group, a guanidine group, and a nitrogen-containing heterocyclic group. Ｎeach independently represents a hydrogen atom or an organic group (a group containing at least one carbon atom). Examples of the nitrogen-containing heterocyclic group include nitrogen-containing aromatic heterocyclic groups such as a pyrrole group, an imidazole group, a pyrazole group, an oxazolyl group, a triazole group, a benzimidazole group, a benztriazole group, a pyridyl group, and a triazine group, and nitrogen-containing aliphatic heterocyclic groups such as a pyrrolidinyl group, a piperidinyl group, and a piperazinyl group, and aromatic heterocyclic groups having 5 or 6 ring atoms such as an imidazole group and a pyridyl group are preferred.

[0028] The basic functional group is preferably an amino group, a hydrazine group, or a guanidine group, more preferably a primary amino group, a secondary amino group, or a tertiary amino group, and even more preferably a primary amino group. When the amino group is a secondary amino group or a tertiary amino group, the number of carbon atoms contained in the secondary amino group or the tertiary amino group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 3.

[0029] The acidic functional group may be a phosphonic acid group (-PO ３ H ２ ), phosphinic acid group (-PO ２ H ２ ), phosphate group (-PO ４ H ２ ), sulfo group (—SO ３ Examples of the alkyl group include a phosphonic acid group, a phosphoric acid group, a phosphinic acid group, a sulfo group, and a carboxy group, and more preferably a phosphonic acid group, a phosphoric acid group, or a sulfo group.

[0030] The specific compound is preferably a compound represented by the following general formula (1), and more preferably a compound represented by the following general formula (2). １ The ClogP of the molecular structure excluding the specific functional group in the specific compound is 10.3 or more. The preferred range of ClogP is the same as the preferred range of ClogP of the molecular structure excluding the specific functional group in the specific compound described above. １The ClogP of each of the molecular structures excluding the specific functional group is 10.3 or greater. The preferred range of ClogP is the same as the preferred range of ClogP of the molecular structure excluding the specific functional group in the specific compound described above. The molecular weight of the compound represented by general formula (1) is 500 to 2000. This molecular weight is preferably 1500 or less, more preferably less than 1500, and even more preferably 1000 or less. The molecular weight of the compound represented by general formula (2) is 500 to 2000. This molecular weight is preferably 1500 or less, more preferably less than 1500, and even more preferably 1000 or less. General formulas (1) and (2) will be described in detail below.

[0031]

[0032] In general formula (1), X １ represents a primary amino group, a phosphonic acid group, a phosphoric acid group, or a sulfo group. １ represents a single bond, —O— or —COO—.

[0033] Y １ represents an aromatic group which may have a substituent. The aromatic ring constituting the aromatic group may be either an aromatic hydrocarbon ring or an aromatic heterocycle, with an aromatic hydrocarbon ring being preferred. The aromatic ring constituting the aromatic group may be either a monocycle or a polycycle. Examples of polycycles include a fused ring formed by condensing two or more monocycles, and a linked ring formed by connecting two or more rings selected from monocycles and fused rings with a single bond. The number of carbon atoms in the aromatic ring constituting the aromatic group is preferably 4 to 30, more preferably 6 to 20, and even more preferably 6 to 15. Specific examples of the aromatic ring constituting the aromatic group include a benzene ring, a naphthalene ring, a pyrene ring, a thiophene ring, an indole ring, a carbazole ring, a benzothiophene ring, a dibenzothiophene ring, a porphyrin ring, a 9,9-bisphenylfluorene ring, and an aromatic ring formed by connecting two or more of these with a single bond.

[0034] Y １Examples of the substituent that the aromatic group represented by the formula (I) may have include an aliphatic hydrocarbon group that may have a substituent. As the aliphatic hydrocarbon group that the aromatic group may have, an aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferred. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The linear or branched aliphatic hydrocarbon group preferably has 4 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 18 carbon atoms. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as adamantane. The cyclic aliphatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 7 to 30 carbon atoms, and even more preferably 8 to 20 carbon atoms. The aliphatic hydrocarbon group may have an oxygen atom or a sulfur atom at the terminal or between carbon atoms. That is, the aliphatic hydrocarbon group may have an ethereal oxygen atom or a thioethereal sulfur atom at the terminal or between carbon atoms. The aliphatic hydrocarbon may further have a substituent (for example, an aromatic group).

[0035] The number of substituents that the aromatic group may have is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0036] n represents an integer of 1 or greater, and is preferably 4 to 30, more preferably 6 to 25, and even more preferably 6 to 20. General formula (2) will be described in detail below.

[0037]

[0038] In general formula (2), X １ represents a primary amino group, a phosphonic acid group, a phosphoric acid group, or a sulfo group. １ represents a single bond, —O— or —COO—.

[0039] L ２ represents a single bond or a (q+1)-valent linking group. ２is a single bond, q represents 1. Examples of the (q+1)-valent linking group include a (q+1)-valent aliphatic hydrocarbon group, a (q+1)-valent aromatic group, —O— (ethereal oxygen atom), —S— (thioethereal sulfur atom), —CO— (carbonyl group), and —NR Ｃ - (R Ｃ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms; -N< (nitrogen atom), and groups formed by combining two or more of these groups.

[0040] The (q+1)-valent aliphatic hydrocarbon group may be linear, branched, or cyclic, but is preferably linear or branched. Examples of the divalent aliphatic hydrocarbon group include an alkylene group, an alkenylene group, and an alkynylene group, with an alkylene group being preferred. The (q+1)-valent aliphatic hydrocarbon group preferably has 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms.

[0041] The (q+1)-valent aromatic group may be either a (q+1)-valent aromatic hydrocarbon group or a (q+1)-valent aromatic heterocyclic group, with an aromatic hydrocarbon group being preferred. The aromatic ring constituting the (q+1)-valent aromatic group may be either a monocyclic or polycyclic ring. Examples of polycyclic rings include fused rings formed by condensing two or more monocyclic rings, and linked rings formed by connecting two or more rings selected from monocyclic and fused rings with a single bond. Specific examples of aromatic rings constituting the (q+1)-valent aromatic group include a benzene ring, a naphthalene ring, a pyrene ring, a thiophene ring, an indole ring, a carbazole ring, a benzothiophene ring, a dibenzothiophene ring, a porphyrin ring, a 9,9-bisphenylfluorene ring, and an aromatic ring formed by connecting two or more of these with a single bond. The number of carbon atoms in the (q+1)-valent aromatic group is preferably 4 to 25, more preferably 6 to 20, and even more preferably 6 to 10.

[0042] The (q+1)-valent aliphatic hydrocarbon group and the (q+1)-valent aromatic group may have a substituent. Examples of the substituent that the (q+1)-valent aliphatic hydrocarbon group may have include a halogen atom. Examples of the substituent that the (q+1)-valent aromatic group may have include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a halogen atom.

[0043] In the above general formula (2), Y ２ represents an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a group formed by combining these. As the aliphatic hydrocarbon group, an aliphatic hydrocarbon group having 1 to 30 carbon atoms is preferable. The aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include an alkyl group, an alkenyl group, and an alkynyl group. The linear or branched aliphatic hydrocarbon group preferably has 4 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 18 carbon atoms. The cyclic aliphatic hydrocarbon group may be a monocyclic ring such as a cyclohexane ring, or a polycyclic ring such as an adamantane ring. The cyclic aliphatic hydrocarbon group preferably has 6 to 30 carbon atoms, more preferably 7 to 30 carbon atoms, and even more preferably 8 to 20 carbon atoms.

[0044] Y ２ Specific examples and preferred embodiments of the aromatic group which may have a substituent represented by the formula: １ Specific examples and preferred embodiments of the aromatic group which may have a substituent represented by the following formula:

[0045] In the general formula (2), n, p, and q each independently represent an integer of 1 or more. ２ When represents a single bond, q represents 1. m represents an integer of 0 or more. n is preferably 4 to 30, more preferably 6 to 25, and still more preferably 6 to 20. p is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. q is preferably 1 to 6, more preferably 1 to 3, and still more preferably 1 or 2. m is preferably 0 to 2, and more preferably 0 or 1.

[0046] The specific compound may be used alone or in combination of two or more. The content of the specific compound is preferably 10.00% by mass or less, more preferably 5.00% by mass or less, and even more preferably 3.00% by mass or less, based on the total mass of the composition. The lower limit is not particularly limited, but is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and even more preferably 0.05% by mass or more. The total amount of the specific compound and the solvent described below is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 99.90% by mass or more, based on the total mass of the composition. The upper limit is 100% by mass or less, and preferably 99.9999% by mass or less.

[0047] [Solvent] The present composition preferably contains a solvent. Examples of the solvent include water and organic solvents, with organic solvents being preferred. Examples of the organic solvent include alcohol-based solvents, ether-based solvents, ester-based solvents, ketone-based solvents, amide-based solvents, sulfur-containing solvents, and hydrocarbon-based solvents.

[0048] Examples of alcohol-based solvents include monoalcohol-based solvents, polyol-based solvents, and glycol monoether-based solvents. Examples of monoalcohol-based solvents include aliphatic monoalcohol-based solvents having 1 to 18 carbon atoms, such as methanol, ethanol (EtOH), 1-propanol, 2-propanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, isopentyl alcohol, and 4-methyl-2-pentanol (methyl isobutyl carbinol); alicyclic monoalcohol-based solvents having 3 to 18 carbon atoms, such as cyclohexanol; aromatic monoalcohol-based solvents, such as benzyl alcohol; and ketone monoalcohol-based solvents, such as diacetone alcohol. Examples of polyol-based solvents include glycol-based solvents having 2 to 18 carbon atoms, such as ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, diethylene glycol, and dipropylene glycol. Examples of glycol monoether solvents include glycol monoether solvents having 3 to 19 carbon atoms, such as propylene glycol monomethyl ether (PGME), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol monoisopropyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, triethylene glycol monobutyl ether, 1-methoxy-2-propanol, 2-methoxy-1-propanol, 1-ethoxy-2-propanol, 2-ethoxy-1-propanol, propylene glycol mono-n-propyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n-propyl ether, tripropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monobenzyl ether, and diethylene glycol monobenzyl ether.The alcohol solvent preferably has 1 to 19 carbon atoms, more preferably 2 to 12 carbon atoms, and even more preferably 3 to 8 carbon atoms.

[0049] Examples of ether solvents include dialkyl ether solvents such as diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, t-butyl methyl ether, dihexyl ether, and cyclohexyl methyl ether; cyclic ether solvents such as tetrahydrofuran and tetrahydropyran; anisole; and diphenyl ether.

[0050] Examples of ester solvents include glycol ester solvents, monocarboxylic acid ester solvents such as n-butyl acetate and ethyl lactate, lactone solvents such as γ-butyrolactone (GBL) and δ-valerolactone, and carbonate solvents such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, and propylene carbonate. Examples of glycol ester solvents include glycol dicarboxylate solvents having 6 to 22 carbon atoms such as ethylene glycol diacetate, diethylene glycol diacetate, triethylene glycol diacetate, tetraethylene glycol diacetate, propylene glycol diacetate, dipropylene glycol diacetate, and methoxybutyl acetate, as well as propylene glycol monomethyl ether acetate (PGMEA), ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, and propylene glycol monomethyl ether acetate. Examples of the ester-based solvent include glycol monoether carboxylate solvents having 5 to 21 carbon atoms, such as ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, tetraethylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, tripropylene glycol monomethyl ether acetate, tetrapropylene glycol monomethyl ether acetate, and butylene glycol monomethyl ether acetate. The number of carbon atoms in the ester-based solvent is preferably 3 to 22, and more preferably 4 to 12.

[0051] Examples of hydrocarbon solvents include aliphatic hydrocarbon solvents such as n-pentane and n-hexane, alicyclic hydrocarbon solvents such as cyclohexane and methylcyclohexane, and aromatic hydrocarbon solvents such as toluene and xylene.

[0052] Examples of ketone solvents include chain ketone solvents such as methyl isobutyl ketone, acetone, methyl ethyl ketone, diethyl ketone, methyl-n-butyl ketone, 2-heptanone, ethyl-n-butyl ketone, methyl-n-ketone, diisobutyl ketone, and trimethylnonane; cyclic ketone solvents such as cyclohexanone, cyclopentanone, cycloheptanone, and methylcyclohexanone; and acetophenone.

[0053] Examples of amide solvents include formamide, monomethylformamide, dimethylformamide, acetamide, monomethylacetamide, dimethylacetamide, monoethylacetamide, diethylacetamide, and N-methylpyrrolidone.

[0054] Examples of sulfur-containing solvents include dimethyl sulfone, dimethyl sulfoxide, and sulfolane.

[0055] The solvent is preferably an alcohol solvent, an ether solvent, an ester solvent, or a ketone solvent, more preferably an aliphatic monoalcohol solvent, a glycol monoether solvent, a glycol ester solvent, a monocarboxylic acid ester solvent, an ether solvent, or a lactone solvent, and even more preferably a glycol monoether solvent or a glycol ester solvent. Among these, the solvent preferably contains at least one selected from the group consisting of PGMEA, PGME, cyclohexanone, ethyl lactate, methyl isobutyl carbinol, EtOH, and γ-butyrolactone, and more preferably contains at least one selected from the group consisting of PGMEA, PGME, cyclohexanone, ethyl lactate, and methyl isobutyl carbinol.

[0056] The solvent may be used alone or in combination of two or more. The content of the solvent is preferably 90.00% by mass or more, more preferably 95.00% by mass or more, and even more preferably 97.00% by mass or more, based on the total mass of the composition. The upper limit is preferably less than 100% by mass, more preferably 99.999% by mass or less, and even more preferably 99.9% by mass or less. The content of one solvent in the composition is preferably 90% by mass or more, more preferably 99% by mass or more, and even more preferably 99.9% by mass or more, based on the total amount of all solvents. The upper limit is not particularly limited and may be 100% by mass.

[0057] [Other Components] The composition may contain other components in addition to the specific compound and the solvent. Examples of the other components include a polymerization inhibitor. Examples of the polymerization inhibitor include a phenolic compound, a quinone compound, a free radical compound, an amine compound, and a phosphine compound.

[0058] [Method for producing the present composition] The method for producing the present composition is not particularly limited, and the composition can be produced, for example, by mixing the above-mentioned components. The order or timing of mixing the components is not particularly limited, and the composition can be produced, for example, by adding the specific compound to a stirrer such as a mixer containing a purified solvent and then thoroughly stirring. In order to achieve better effects of the present invention, it is preferable that the raw materials of the present composition (e.g., the solvent and the specific compound) have been subjected to a purification treatment.

[0059] The production process of the present composition may include a step selected from the group consisting of a distillation step of distilling raw materials, a dehydration step of dehydrating the present composition, a metal removal step of removing metal components from the present composition, a filtration step of filtering the present composition, and a destaticization step of destaticizing the present composition.

[0060] This composition can be filled into a known container for storage, transportation, and use. As a container, a container with a high degree of cleanliness within the container for semiconductor applications and which suppresses the elution of impurities from the inner wall of the container's storage section into each liquid is preferred. Examples of such containers include various containers commercially available as containers for semiconductor processing liquids, such as the "Clean Bottle" series manufactured by Aicello Chemical Co., Ltd. and the "Pure Bottle" manufactured by Kodama Resin Industry Co., Ltd., but are not limited to these. Furthermore, the containers exemplified in paragraphs

[0121] to

[0124] of WO 2022 / 004217 can also be used as containers, and the contents of these containers are incorporated herein.

[0061] [Uses of the Composition] The composition is a composition for semiconductor device processing, and is preferably used for modifying a substrate in the manufacturing process of a semiconductor device. In the above process, the composition is used to form a coating that inhibits film formation by atomic layer deposition, thereby obtaining a modified substrate having a coating formed on the substrate surface. The composition is also preferably used for manufacturing a laminate in which a material is deposited in areas where no coating has been formed by ALD processing of the modified substrate. Methods for manufacturing a modified substrate and a laminate will be described in detail below.

[0062] <Substrate> The substrate is not particularly limited, but preferably has at least one of a metal surface A made of a material containing metal atoms and a non-metal surface B made of a non-metal material, and more preferably has a metal surface A.

[0063] The metal atoms contained in the metal surface A are not particularly limited, but are preferably tungsten atoms, copper atoms, ruthenium atoms, cobalt atoms, titanium atoms, tantalum atoms, molybdenum atoms, germanium atoms, zirconium atoms, aluminum atoms, tin atoms, nickel atoms, palladium atoms, indium atoms, zinc atoms, gold atoms, silver atoms, or platinum atoms, more preferably tungsten atoms, ruthenium atoms, molybdenum atoms, copper atoms, or cobalt atoms, and even more preferably tungsten atoms or copper atoms. The form of the metal atoms in the metal surface A is not particularly limited, but includes elemental metals, alloys, nitrides, oxides, and silicides, with elemental metals or alloys being preferred. Examples of alloys include alloys containing two or more of the metal atoms contained in the metal surface A described above. The method for forming the metal surface A is not particularly limited, and known methods can be used. For example, CVD, plating, and physical vapor deposition methods can be used.

[0064] Examples of non-metallic materials constituting the non-metallic surface B include insulators, such as non-metallic elements such as silicon and carbon, non-metallic oxides such as silicon oxide, non-metallic nitrides such as silicon nitride, non-metallic oxynitrides such as silicon oxynitride, and organic materials. The material constituting the non-metallic surface B is preferably a non-metallic material containing silicon atoms, more preferably silicon or silicon oxide. Specific examples of silicon oxide include SiO ｙ (wherein y is preferably 0.5 to 2.0, more preferably 1.0 to 2.0), and SiO ｚ C ｗ (wherein z is preferably 0.5 to 2.0, more preferably 1.0 to 2.0, and w is preferably 0.5 to 2.0, more preferably 1.0 to 2.0). ｙ and SiO ｚ C ｗ The material represented by the composition may further contain hydrogen. ｚ C ｗ Examples of the material represented by the composition include Si(OC ２ H ５ ) ４(tetraethyl orthosilicate, TEOS). Silicon oxides include SiO ２ A material represented by the formula (silicon dioxide) or TEOS is preferred.

[0065] The method for forming the nonmetallic surface B is not particularly limited, and examples thereof include CVD, physical vapor deposition, plasma irradiation, and application of a precursor compound. It is also preferable that the nonmetallic surface B is a surface treatment performed on a region made of silicon or silicon oxide. Examples of the treatment include contact with a treatment liquid such as an aqueous solution containing an acidic compound (preferably hydrogen fluoride water), plasma treatment, corona treatment, and ozone treatment.

[0066] It is also preferable that the substrate has at least two types of surfaces, a first surface and a second surface, which are made of different materials. The first surface is a surface that interacts with a specific functional group of the specific compound. The second surface may be made of a material different from the first surface, but is preferably a surface on which no coating is formed when it comes into contact with the composition. In particular, it is preferable that at least one of the first surface and the second surface is a metal surface A or a non-metal surface B, and it is more preferable that at least one of the first surface and the second surface is a metal surface A. In particular, it is preferable that the first surface is a metal surface made of at least one metal selected from copper, cobalt, tungsten, molybdenum, and ruthenium.

[0067] A preferred embodiment of the substrate is embodiment 1, in which the first surface is a metal surface A. In embodiment 1, the specific functional group possessed by the specific compound is the specific functional group A described above. In embodiment 1, the metal atoms contained in the metal surface A, which is the first surface, are preferably contained in the form of a metal element, an alloy, a conductive metal nitride, or a metal silicide, and more preferably a metal element or an alloy. Examples of the metal element and alloy include the metal elements and alloys thereof exemplified as the metals contained in the metal surface A. Examples of the conductive metal nitride include tantalum nitride, titanium nitride, iron nitride, and aluminum nitride. Examples of the metal silicide include iron silicide, molybdenum silicide, and tungsten silicide.

[0068] In Aspect 1, the second surface is preferably a metal surface A or a non-metal surface B different from the first surface, more preferably a non-metal surface B. In Aspect 1, the metal atoms contained in the metal surface A constituting the second surface are preferably in the form of a metal oxide, a metal nitride, or a metal oxynitride, more preferably a metal oxide. Examples of metal oxides include aluminum oxide, tantalum oxide, iron oxide, and copper oxide.

[0069] A preferred embodiment of the substrate also includes embodiment 2, in which the first surface is a non-metallic surface B. In embodiment 2, the specific functional group possessed by the specific compound is the above-described specific functional group B. In embodiment 2, the second surface is preferably a metallic surface A. In embodiment 2, the metal atoms contained in the second surface, that is, the metallic surface A, are preferably contained in the form of an elemental metal, an alloy, a conductive metal nitride, or a metal silicide, and more preferably in the form of an elemental metal or an alloy.

[0070] The shape of the first surface and the second surface is not particularly limited, and examples thereof include a planar shape, a dotted shape, and a striped shape.

[0071] The shape of the substrate is not particularly limited, and any shape of substrate generally used as a semiconductor substrate can be used. The substrate may be a substrate having the above-described surface, and may be a single-layer or multi-layer structure.

[0072] <Coating> The coating formed on a substrate using the present composition is a coating containing components other than the solvent contained in the composition (e.g., a specific compound). The coating preferably functions as a mask when depositing a material in an ALD process. That is, when an ALD process is performed on a modified substrate on which a coating using the present composition has been formed on a specific region, the material preferably does not deposit in the region where the coating has been formed, but deposits in the region where the coating has not been formed, forming a film (hereinafter also referred to as an "ALD film"). This results in a laminate in which an ALD film is selectively formed in regions other than the region where the coating has been formed.

[0073] The coating also preferably functions as a mask when forming a metal-containing film by chemical vapor deposition (CVD) other than ALD. That is, in a CVD process, deposition of a film by CVD (hereinafter also referred to as a "CVD film") can be suppressed in the region where the coating is formed, and a CVD film can be deposited in the region where the coating is not formed. This results in a laminate in which a CVD film is selectively formed in the region other than the region where the coating is formed. Examples of CVD other than ALD that can be preferably applied to the modified substrate include known techniques such as thermal CVD and plasma CVD. As raw materials for the CVD film used in the CVD process, raw materials for the ALD film described below can be used.

[0074] The thickness of the coating is preferably 0.1 to 100.0 nm, more preferably 0.5 to 50.0 nm, and even more preferably 3.0 to 30.0 nm.

[0075] In order to obtain superior effects of the present invention, the water contact angle of the coating is preferably 60° or more, more preferably 80° or more, and even more preferably 90° or more. There is no particular upper limit, and it is often 120° or less. The water contact angle is the average value of three measurements of the contact angle 500 milliseconds after a water droplet contacts the surface of the measurement object using a contact angle meter (DMs-501, manufactured by Kyowa Interface Science Co., Ltd.).

[0076] [Method for Producing a Modified Substrate] The method for producing a modified substrate of the present invention includes a step of contacting a substrate with the present composition to form a coating on the substrate. This results in a modified substrate having a coating formed on the substrate. The method for producing a modified substrate of the present invention can be suitably used, for example, in the production of electronic devices (semiconductor devices). The method for contacting a substrate with the present composition is not particularly limited, and known methods can be used. Examples include a method of applying (e.g., spin coating) or spraying the present composition onto a substrate, and a method of immersing a substrate in the present composition. When immersing a substrate in the present composition, the present composition may be subjected to convection. The temperature of the present composition when contacting the substrate with the present composition is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. The time for contacting the substrate with the present composition is also not particularly limited, but is preferably 30 seconds to 1 hour, more preferably 30 seconds to 30 minutes, and even more preferably 5 to 15 minutes.

[0077] After contacting the substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and known methods can be used, such as an oven or a hot plate. The heating temperature is preferably 50 to 400°C, more preferably 100 to 350°C, even more preferably 130 to 300°C, and particularly preferably 150 to 250°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 1 to 30 minutes, and even more preferably 3 to 10 minutes.

[0078] After contacting the substrate with the composition, it is also preferable to perform a rinsing treatment. The rinsing treatment can remove at least one of the composition and impurities adhering to regions on the substrate other than the desired region (e.g., the region that interacts with the specific functional group contained in the specific compound) from the substrate. The rinsing method is not particularly limited, and examples include a method of contacting the substrate with a rinsing liquid. As the contacting method, the same method as the method of contacting the substrate with the composition can be used. The temperature of the rinsing liquid during contact is not particularly limited, but is preferably 0 to 50°C, more preferably 10 to 30°C. As the rinsing liquid, a known organic solvent can be used, such as the alcohol-based solvents, ether-based solvents, and ester-based solvents described above.

[0079] [Method for Producing Laminate] The method for producing a laminate of the present invention includes step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each made of a different material (hereinafter also referred to as a "specific substrate") with the present composition to form a first coating on the first surface, and step 2 of subjecting the substrate obtained in step 1 to an ALD treatment to form a second coating on the second surface. This results in a laminate having a second coating (ALD film) on the second surface.

[0080] [Step 1: Method for producing modified substrate] Step 1 is a step of bringing a specific substrate into contact with the present composition to form a first coating on the first surface. Step 1 results in a modified substrate 1 in which a first coating is formed on the first surface of the specific substrate. The first coating is a coating containing the specific compound contained in the present composition. There are no particular limitations on the method for bringing the specific substrate into contact with the present composition, and the method of bringing the present composition into contact with the substrate in the above-mentioned method for producing a modified substrate can be used.

[0081] After contacting the specific substrate with the composition, the coating film may be subjected to a heat treatment. The heating method is not particularly limited, and the heating methods in the above-mentioned method for producing a modified substrate can be used.

[0082] It is also preferable to perform a rinse treatment on the modified substrate 1 having the first coating formed on the first surface. The rinse treatment can remove at least one of the composition and impurities adhering to regions other than the first surface (e.g., the second surface) of the specific substrate from the specific substrate. The rinse method can be the same as the rinse method in the method for producing a modified substrate described above.

[0083] [Step 2: ALD Treatment] Step 2 is a step of subjecting the modified substrate 1 obtained in step 1 to ALD treatment to form a second coating on the second surface. Step 2 results in a laminate 1 having a first coating formed on the first surface and a second coating formed on the second surface. The second coating is a film formed by ALD treatment (ALD film). Note that the modified substrate 1 may be any substrate having a first coating formed on the first surface of the specific substrate in step 1, and may be subjected to the above-mentioned heating treatment, rinsing treatment, etc. after step 1.

[0084] The ALD process method is not particularly limited, and known methods can be used. For example, a method can be used in which a precursor gas serving as a raw material for the ALD film is supplied to the surface of the modified substrate 1, and then the raw material is decomposed and / or chemically reacted with an oxidizing agent or a reducing agent, etc., to deposit the material, thereby forming an ALD film. The precursor is not particularly limited, and known precursors can be used depending on the type of ALD film to be formed, such as organometallic compounds. Examples of precursors that can be used include alumina, tantalum nitride, and titanium nitride. The oxidizing agent is not particularly limited, and known oxidizing agents used in ALD processes can be used, such as water, oxygen, and ozone.

[0085] The materials constituting the ALD film can be controlled by the type of precursor supplied, the supply atmosphere, the oxidizing agent, etc. The materials of the formed ALD film are not particularly limited, and include metals, metal oxides, and metal nitrides. Examples of metals include aluminum, titanium, chromium, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, ruthenium, palladium, lanthanum, cerium, hafnium, tantalum, tungsten, platinum, and bismuth. Examples of metal oxides include aluminum oxide, titanium oxide, zinc oxide, zirconium oxide, hafnium oxide, and tantalum oxide. Examples of metal nitrides include titanium nitride and tantalum nitride. In the ALD process, a treatment for modifying the surface of the region where the first coating is not formed may be performed.

[0086] After the ALD process, the thickness of the material deposited on the first coating is preferably as thin as possible, preferably 4.0 nm or less, more preferably 2.0 nm or less, and even more preferably 1.0 nm or less. The lower limit is 0 nm. The ratio of the thickness of the material deposited on the region where the first coating is formed to the thickness of the second coating is preferably 0.75 or less, more preferably 0.50 or less, and even more preferably 0.25 or less. The lower limit of the ratio is 0 or more.

[0087] [Step 3: Removal of Coating (Removal Treatment)] The method for producing a laminate of the present invention may include, after step 2, step 3 of removing the first coating formed on the first surface in step 1. Step 3 results in a laminate 2 that has no coating on the first surface and has the second coating on the second surface.

[0088] The method for removing the first coating is not particularly limited, and examples thereof include dry etching, wet etching, and a combination thereof. As dry etching, known methods can be used, such as chemical dry etching, which supplies reactive ions or reactive radicals to the surface of the laminate 1, and physical dry etching, such as sputter etching and ion beam etching. Among these, removal by plasma treatment is preferred. As wet etching, a method in which an etching solution is supplied to the laminate 1 can be used. Examples of the etching solution include etching solutions containing oxidizing agents such as ozone and hydrofluoric acid, and etching solutions containing an organic solvent. Examples of the organic solvent include the organic solvents contained in the above-mentioned chemical solutions, and alcohol-based solvents, ester-based solvents, ketone-based solvents, and hydrocarbon-based solvents are preferred.

[0089] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below. The preparation, filling, storage, etc. of the composition were all carried out in a clean room meeting ISO Class 2 or lower. Furthermore, the containers used for the preparation, filling, storage, etc. of the composition were washed with the solvent used in the preparation or the prepared composition before use.

[0090] [Synthesis of Specific Compound E-1] Specific compound E-1 was synthesized as follows.

[0091]

[0092] [Synthesis of Intermediate E-1A] Under a nitrogen flow (50 mL / min), 11-bromo-1-undecene (10.0 g, 42.9 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a three-neck flask and cooled to 0°C. Next, 9-BBN (0.5 M in THF (tetrahydrofuran) solution, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added dropwise, and the mixture was stirred at room temperature for 2 hours. After further stirring at 60°C for 2 hours, the mixture was cooled to room temperature, and an aqueous NaOH solution (2.0 M, 126 mL), tetrakistriphenylphosphine palladium (2.4 g, 2.0 mmol, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 5-bromo-1,2,3-tris(dodecyloxy)benzene (29.0 g, 40.8 mmmol, manufactured by Tokyo Chemical Industry Co., Ltd.) were added. The reaction solution obtained above was stirred at 75°C for 18 hours. After completion of the reaction, the reaction solution was filtered through Celite, and methylene chloride (200 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was added to extract the organic layer. The organic layer was then washed with distilled water (200 mL) and saturated brine (200 mL) and concentrated under reduced pressure to remove the organic solvent. The obtained crude product was purified by silica gel column chromatography to obtain intermediate E-1A.

[0093] [Synthesis of Intermediate E-1B] Under a nitrogen flow (0.1 L / min), intermediate E-1A (5.0 g, 5.7 mmol), potassium phthalimide (2.4 g, 12.7 mmol, manufactured by Tokyo Chemical Industry Co., Ltd.), and DMF (dimethylformamide, 25 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were placed in a three-neck flask and stirred at 50°C for 3 hours. After completion of the reaction, the solid was removed by filtration, and ethyl acetate (100 mL, manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and distilled water (100 mL) were added to extract the organic layer. Next, the organic layer was concentrated under reduced pressure, and the solvent was distilled off from the resulting organic layer to obtain intermediate E-1B.

[0094] [Synthesis of Specific Compound E-1] Under a nitrogen flow (0.1 L / min), intermediate E-1B (4.00 g, 4.3 mmol), ethanol (50 mL, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), and THF (5 mL, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) were added to a three-neck flask and stirred. Hydrazine monohydrate (0.86 g, 17.2 mmol, manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) was added to the resulting mixture, and the mixture was heated to reflux for 1 hour. After completion of the reaction, the solid was removed by filtration, and the reaction solution was concentrated under reduced pressure to distill off the solvent. Subsequently, 1 M aqueous sodium hydroxide solution (100 mL) was added to the obtained crude product, followed by stirring and filtration. The obtained solid was further washed with distilled water (100 mL) to obtain Specific Compound E-1.

[0095] Specific compounds other than the specific compound E-1 were synthesized in accordance with the synthesis method for the specific compound E-1, while appropriately adjusting the raw materials and reaction conditions so as to obtain the specific compounds shown below.

[0096] The materials used in preparing the compositions of the examples and comparative examples are shown below. The comparative compound CE-2 was a high molecular weight compound having repeating units, and had a number average molecular weight of 4,800 and a weight average molecular weight of 5,100.

[0097] [Specific compound]

[0098]

[0099]

[0100]

[0101]

[0102] [Comparative Compounds]

[0103]

[0104] [Solvent] PGME: Propylene glycol monomethyl ether PGMEA: Propylene glycol monomethyl ether acetate IPA: Isopropyl alcohol

[0105] [Liquid Preparation] Compositions of each of the Examples and Comparative Examples were prepared by mixing the specific compound or comparative compound with a solvent so as to obtain the composition shown in the table below.

[0106] [Preparation of modified substrate] A commercially available silicon wafer (diameter 12 inches) was prepared as a substrate. A tungsten (W) layer, a ruthenium (Ru) layer, a molybdenum (Mo) layer, a copper (Cu) layer, and a cobalt (Co) layer were formed on one surface of the silicon wafer, respectively, to prepare a W-layer wafer, a Ru-layer wafer, a Mo-layer wafer, a Cu-layer wafer, and a Co-layer wafer (hereinafter, these are also collectively referred to as "layered wafers"). The W layer, Ru layer, and Mo layer were formed by CVD, and the Cu layer and Co layer were formed by sputtering. The film formation conditions were adjusted so that the thickness of each layer was 20 nm. The silicon wafer and each layered wafer were cut into 2 cm squares and washed by immersion in isopropyl alcohol (IPA). The cleaning was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25° C., and the cleaning time was 30 seconds. After cleaning, the wafer was dried by blowing nitrogen gas onto it, thereby preparing an unmodified substrate.

[0107] Next, each unmodified substrate after cleaning was immersed in each composition to perform a modification treatment on the substrate. The immersion was performed while stirring the composition at a stirring speed of 250 rpm, the composition temperature was 25°C, and the immersion time was 10 minutes. After immersion, each substrate was rinsed by immersing it in IPA. The rinsing treatment was performed while stirring the IPA at a stirring speed of 250 rpm, the IPA temperature was 25°C, and the rinsing time was 30 seconds. After rinsing, the wafer was dried by spraying nitrogen gas. A modified substrate was obtained by the above procedure.

[0108] [Evaluation] [Evaluation of ALD Inhibition (Deposition Inhibition)] A tantalum nitride (TaN) layer (ALD film) was formed by ALD using an atomic layer deposition system (AD-230LP, manufactured by Samco) on each of the modified substrates (wafers with each layer) obtained by [Preparation of Modified Substrate] and on the substrates (unmodified substrates: Comparative Examples CA1 to CE1) before immersion in each composition. PDMAT (pentakis(dimethylamino)tantalum) was used as the organometallic source and ammonia as the reducing agent, and the ALD treatment temperature was 300°C. Other conditions were adjusted so that the thickness of the ALD film formed on the unmodified substrate would be 5 nm. For example, in Table 1, an ALD film was formed on the modified substrate under conditions such that the thickness of the ALD film formed on the W layer wafer before immersion in the composition would be 5 nm. The thickness of the ALD film of each sample after ALD processing was measured using an X-ray fluorescence (XRF) analyzer (AZX400 manufactured by Rigaku Corporation). Measurements were performed at five points on the substrate, and the average value was taken as the film thickness. From the obtained film thickness, ALD inhibition (deposition inhibition) was evaluated according to the following evaluation criteria. The smaller the film thickness, the more difficult it is for a film to deposit by ALD processing, i.e., the better the ALD inhibition. ALD inhibition of F or higher is preferable, with S being most preferable.

[0109] (Evaluation criteria) S: The thickness of the ALD film is less than 0.3 nm. A: The thickness of the ALD film is 0.3 nm or more and less than 0.5 nm. B: The thickness of the ALD film is 0.5 nm or more and less than 1.0 nm. C: The thickness of the ALD film is 1.0 nm or more and less than 1.3 nm. D: The thickness of the ALD film is 1.3 nm or more and less than 1.7 nm. E: The thickness of the ALD film is 1.7 nm or more and less than 2.0 nm. F: The thickness of the ALD film is 2.0 nm or more and less than 2.5 nm. G: The thickness of the ALD film is 2.5 nm or more and less than 3.0 nm. H: The thickness of the ALD film is 3.0 nm or more.

[0110] [Evaluation of Removability of Composition After Evaluation of ALD Inhibition] After the evaluation of ALD inhibition (deposition inhibition), the composition of the Example or Comparative Example on each modified substrate (wafer with each layer) was removed using a hydrogen plasma exposure device (GIGA 80 Plus, manufactured by PVA TePla). The hydrogen plasma exposure was carried out under the following conditions: ２ / Ar=40:10 sccm, ICP: 350 W, RF: 10 W, 350°C-10 min. The amount of composition remaining on each modified substrate after the hydrogen plasma exposure was measured using an X-ray photoelectron spectroscopy (XPS) device (JPS-9030, manufactured by JEOL Ltd.). Specifically, the carbon content of the unmodified substrate and the modified substrate after hydrogen plasma exposure was measured by the XPS measurement, and the amount of remaining composition was calculated using the following formula: remaining amount of composition (%) = carbon content of modified substrate after hydrogen plasma exposure (%) - carbon content of unmodified substrate (%). The composition removability was evaluated using the obtained remaining amount of composition according to the following evaluation criteria. The smaller the remaining amount of composition, the more the composition has been removed by the hydrogen plasma exposure treatment, i.e., the better the composition removability. A rating of A or higher is preferred, with S being most preferred.

[0111] (Evaluation Criteria) S: The remaining amount of the composition is 5% or less. A: The remaining amount of the composition is 5% or more and less than 10%. B: The remaining amount of the composition is 10% or more.

[0112] [Results] The composition and evaluation results of each composition are shown in Tables 1 to 5. Table 1 shows the results assuming a W layer as the first surface, Table 2 shows the results assuming a Mo layer as the first surface, Table 3 shows the results assuming a Ru layer as the first surface, Table 4 shows the results assuming a Cu layer as the first surface, and Table 5 shows the results assuming a Co layer as the first surface.

[0113] In the tables, the "amount (parts by mass)" of the specific compound or comparative compound represents the content (unit: parts by mass) of the specific compound or comparative compound when the total mass of the composition is 100 parts by mass. In tables, when the composition contains a solvent, the content of the solvent is the remainder after subtracting the content of the specific compound or comparative compound from the total mass of the composition. In tables, the numerical value in the "ClogP" column indicates the ClogP value of the structure of the specific compound other than the specific functional group. In tables, the numerical value in the "Mw" column indicates the molecular weight of the specific compound. However, in Comparative Example CA3, it indicates the weight average molecular weight of Comparative Compound CE-2. In tables, the numerical value in the "pKa" column indicates the acid dissociation constant of the conjugate acid of the specific compound obtained by adding a proton to the basic functional group when the specific functional group is a basic functional group, and indicates the acid dissociation constant of the specific compound when a proton dissociates from the acidic functional group when the specific functional group is an acidic functional group. The methods for calculating molecular weight, ClogP, and acid dissociation constant are as described above.

[0114]

[0115]

[0116]

[0117]

[0118]

[0119]

[0120]

[0121] The results in Tables 1 to 5 confirm that the composition of the present invention has excellent ALD inhibitory properties and can form a coating that is easily removed by a removal treatment after ALD processing. Furthermore, a comparison between Examples A2 and A3 and the like confirmed that, for a specific compound, when the specific functional group is a basic functional group, and the basic functional group is an amino group, a hydrazine group, or a guanidine group, the ALD inhibitory properties are even better. A comparison between Examples A3 and A4 and the like confirmed that, for a specific compound, when the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group, the ALD inhibitory properties are even better. A comparison between Examples A6 and A7 and the like confirmed that, for a specific compound, when the basic functional group is a primary amino group, the ALD inhibitory properties are even better. A comparison between Examples A4 and A5 and the like confirmed that, when the molecular weight of the specific compound is 500 or more, the ALD inhibitory properties are even better. Comparisons of Examples A14 and A27 with other Examples confirmed that when the molecular weight of the specific compound is 1000 or less, the composition removability after ALD treatment is superior. Comparisons of Examples A5 and A6 confirmed that when the specific compound has both an aliphatic hydrocarbon structure and an aromatic ring structure, the ALD inhibitory properties are superior. Comparisons of Examples A7 and A8 confirmed that when the specific compound is a compound represented by general formula (1), the ALD inhibitory properties are superior. Comparisons of Examples A1 and A8 confirmed that when the specific compound is a compound represented by general formula (2), the ALD inhibitory properties are superior. Comparisons of Examples D2 and D3 confirmed that when the specific functional group is an acidic functional group, and the acidic functional group is a phosphonic acid group, a phosphate group, or a sulfo group, the ALD inhibitory properties are superior.

Claims

1. A composition for semiconductor device processing, comprising a compound having at least one specific functional group that interacts with a substrate, wherein the molecular weight of the compound is 2000 or less, the ClogP of the molecular structure of the compound excluding the specific functional group is 10.3 or more, the specific functional group is a basic functional group or an acidic functional group, and when the specific functional group is the basic functional group, the acid dissociation constant of the conjugate acid of the compound obtained by adding a proton to the basic functional group is 7.0 or more, and when the specific functional group is the acidic functional group, the acid dissociation constant of the compound when a proton dissociates from the acidic functional group is 5.0 or less.

2. The composition for semiconductor device processing of claim 1, further comprising a solvent.

3. The composition for treating a semiconductor device according to claim 1, wherein the specific functional group is the basic functional group, and the basic functional group is an amino group, a hydrazine group, or a guanidine group.

4. The composition for treating semiconductor devices according to claim 3, wherein the basic functional group is a primary amino group, a secondary amino group, or a tertiary amino group.

5. The composition for treating semiconductor devices according to claim 4, wherein the basic functional group is a primary amino group.

6. The composition for treating a semiconductor device according to claim 1, wherein the specific functional group is the acidic functional group, and the acidic functional group is a phosphonic acid group, a phosphoric acid group, a phosphinic acid group, a sulfo group, or a carboxy group.

7. The composition for treating a semiconductor device according to claim 6, wherein the acidic functional group is a phosphonic acid group, a phosphoric acid group, or a sulfo group.

8. The composition for treating semiconductor devices according to claim 1, wherein the compound has a molecular weight of 500 or more.

9. The composition for treating a semiconductor device according to claim 1, wherein the compound has at least one of an aliphatic hydrocarbon structure and an aromatic ring structure.

10. The composition for processing semiconductor devices according to claim 1, wherein the compound has both an aliphatic hydrocarbon structure and an aromatic ring structure.

11. The compound is a compound represented by general formula (1), and X in the compound represented by general formula (1) １ 2. The composition for treating semiconductor devices according to claim 1, wherein the molecular structure excluding (a) has a ClogP of 10.3 or more, and the molecular weight of the compound represented by general formula (1) is 500 to 2000. In general formula (1), X １ represents a primary amino group, a phosphonic acid group, a phosphoric acid group, or a sulfo group. １ represents a single bond, —O— or —COO—. １ represents an aromatic group which may have a substituent, and n represents an integer of 1 or more.

12. The compound is a compound represented by general formula (2), and X in the compound represented by general formula (2) １ 2. The composition for treating semiconductor devices according to claim 1, wherein the molecular structure excluding (a) has a ClogP of 10.3 or more, and the molecular weight of the compound represented by general formula (2) is 500 to 2000. In formula (2), X １ represents a primary amino group, a phosphonic acid group, a phosphoric acid group, or a sulfo group. １ represents a single bond, —O— or —COO—. ２ represents a single bond or a (q+1)-valent linking group. ２ represents an aliphatic hydrocarbon group which may have a substituent, an aromatic group which may have a substituent, or a group formed by combining these; n, p, and q each independently represent an integer of 1 or more. ２ When is a single bond, q represents 1. m represents an integer of 0 or more.

13. The composition for treating semiconductor devices according to claim 2, wherein the total amount of the compound and the solvent is 99.90% by mass or more based on the total mass of the composition for treating semiconductor devices.

14. The composition for treating semiconductor devices according to claim 1, wherein the film obtained by applying the composition for treating semiconductor devices has a water contact angle of 60 degrees or more.

15. A method for producing a modified substrate, comprising the step of contacting a substrate with a composition for treating a semiconductor device according to any one of claims 1 to 14, thereby forming a coating on the substrate.

16. A method for producing a laminate, comprising: step 1 of contacting a substrate having at least two surfaces, a first surface and a second surface, each surface being made of a different material, with a composition for treating semiconductor devices according to any one of claims 1 to 14 to form a first coating on the first surface; and step 2 of subjecting the substrate obtained in step 1 to atomic layer deposition to form a second coating on the second surface.

17. The method for producing a laminate according to claim 16, wherein the first surface is a metal surface composed of at least one metal selected from copper, cobalt, tungsten, molybdenum, and ruthenium.

18. A method for producing an electronic device, comprising the method for producing the modified substrate according to claim 15.

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